Lead-free perovskite ceramics with ultraviolet-tunable optical and magnetic properties at room temperature

Abstract

Potassium sodium niobate (KNN) is a lead free ceramic that can potentially replace PZT (Pb(ZrTi)O3). However, KNN suffers from a few major disadvantages. These include the presence of highly volatile alkaline elements and stoichiometry sensitive properties coupled with severe difficulties in controlling the composition. In this work, La doped sodium potassium niobate based perovskite (ABO3) ceramics, more specifically [{(1-x)(K0.5Na0.5)xLa}Nb(1–2x/5)O3] (0 < x < 0.1), have been developed. Among these, the material at 5 mol. % La doping appears with an unusually high density up to 99% of its theoretical value, while densities of the parent K0.5N0.5NbO3 (KNN) ceramics typically only reach ∼70% to 89% of the theoretical limit. The developed ceramics in their circular and rectangular disk form with thickness 0.8 mm show transparency and most importantly, this transparency is electrically tunable up to 52%. Additionally, the material shows sensitivity of its magnetic and optical properties to ultraviolet (UV) irradiation, i.e., these materials transform to a metastable and reversible state that exhibits graded color change from clear to deep blue and shows a considerable increase in magnetization under UV exposure. This feature makes the developed ceramics attractive for the fabrication of new generation devices; e.g., powerless UV detectors as well as protectors, since it absorbs UV completely. Based on first-principles calculations, we developed a model that attributes these observations to the occupancy of La fxyz orbitals induced by UV excitations. The model also indicates that UV induced absorption in the visible range and magnetism are related.